CN103534867B - Ionic liquid containing sulfonate ions - Google Patents

Ionic liquid containing sulfonate ions Download PDF

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CN103534867B
CN103534867B CN201280023680.8A CN201280023680A CN103534867B CN 103534867 B CN103534867 B CN 103534867B CN 201280023680 A CN201280023680 A CN 201280023680A CN 103534867 B CN103534867 B CN 103534867B
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ionic liquid
cation
metal
ion
root
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CN103534867A (en
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D·沃尔菲
C·A·弗里森
P·B·约翰森
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Influent Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/023—Gel electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Embodiments are related to ionic liquids and more specifically to ionic liquids used in electrochemical metal-air cells in which the ionic liquid includes sulfonate ions as the anion.

Description

Ionic liquid containing sulfonate ion
The present invention is the contract number subsidized by Ministry of Energy to complete under the governmental support of DB-AR0000038.U.S. government Have certain rights in the invention.This application claims the provisional application 61/498,308 of the submission of on June 17th, 2011 is excellent First weigh, disclosure of which here is fully incorporated herein by reference.
Invention field
Embodiments of the present invention are related to ionic liquid, more particularly relate to electrochemical metal-air cell from Sub- liquid, wherein the ionic liquid includes sulfonate ion.
Background
For the notable infringement of the energy density of most of batteries is caused by the negative electrode of battery.For using such as lithium Or the battery chemistries of nickel, this is real.Generally, oxidant is deposited in negative electrode with mole charging capacity less than two to five times of anode Storage.On the other hand, many fuel cells use the oxygen in air as the source of oxidant.Continuous and virtually limitless oxidant The presence in source causes to be capable of achieving high-energy-density in principle.However, due to steam pressure and the complexity problem of system balance（Example Such as the problem of moist and film）, the use of hydrogen and organic-fuel hinders energy-efficient.Metal-air electrochemical cell can It is related to modern energy demand big to realize with reference to the superelevation anode capacity and the air breathing formula negative electrode of fuel cell of battery The energy density of amount.
Metal-air battery typically comprises the fuel electrode that metal fuel is oxidized wherein, oxygen and is reduced wherein Air electrode, and for providing the electrolyte of ionic conductivity.The limiting factor of conventional metals-air cell is that electrolyte is molten The evaporation of liquid（That is ion conducting medium）, the water in the particularly evaporation of solvent, such as aqueous electrolyte solution.Due to requiring air Electrode is air-impermeable to absorb oxygen, so it can also allow solvent vapour such as vapor to escape from battery.With Time passage, due to the consumption of solvent, battery becomes effectively to work.In fact, in many battery designs, the steaming Question is inscribed and battery can not be worked before fuel is consumed.Secondary（That is, can fill）In battery, the evaporation problems aggravation, Because repeatedly can again fill fuel within the life-span of battery, and electrolyte solution can not（Lack the supplement from external source）.
Also related to traditional aqueous electrolyte cell other problemses, such as in charging process the electrolysis of water and from Electric discharge.In charging process, electric current passes through battery to reduce the oxygenated fuel at fuel electrode.However, some electric current electricity Xie Shui causes the liberation of hydrogen on fuel electrode（Reduction）With the analysis oxygen on oxygen electrode（Oxidation）, it is shown below：
(1) reduce:2H2O(l)+2e-→H2(g)+2OH-(aq)
And
(2) aoxidize:2H2O(l)→O2(g)+4H+(aq)+4e-
By this way, aqueous electrolyte further loses from battery.Additionally, the electronics consumed when protohydrogen is gone back is not yet Can be used to reduce oxidized thing.Therefore, the parasitic electrolysis (parasitic electrolysis) of aqueous electrolyte reduces The cycle efficieny of secondary cell.
Self discharge may originate from the impurity in electrode or the reaction with electrolyte.Usually from the self discharge of impurity in electrode It is little（The monthly loss of 2-3%）.However, active metal is possibly at a relatively high with the reaction of water and/or the oxygen being dissolved in the water 's（Monthly 20% to 30%）.
In order to make up this problem, the metal-air battery with aqueous electrolyte solution is typically designed to comprising relatively high The electrolyte solution of volume.Some battery designs even introduce for from the device of neighbouring reservoir electrolyte supplement to maintain electrolysis Matter level.However, either method increased the overall dimension and battery weight of battery, without improving battery performance（Except Guarantee there is substantial amounts of electrolyte solution to make up the evaporation of water or other solvents with the time）.Specifically, it is generally special by fuel Property, electrode characteristic, electrolyte characteristics and can be used to react the amount of the electrode surface area for occurring determining battery performance.But it is electric The volume of electrolyte solution does not generally have a significant advantageous effects to battery performance in pond, and therefore generally based on volume and Weight rate（Power ratio volume or weight and energy ratio volume or weight）Aspect only reduces battery performance.In addition, excessive Electrolyte volume can in-between the electrodes produce larger amount of spacing, and this can increase ohmage and reduce performance.
For electrochemical cell it has been proposed that using nonaqueous systems（See, for example, United States Patent (USP) 5827602）.Non-aqueous In gonosome system, aqueous electrolyte can be replaced by ionic liquid.It is well known, however, that containing such as AlCl3Strong Lewis acid ion Liquid is when by time of tide release toxic gas.
The low temperature used in metal-air electrochemical cell or ionic liquid at room temperature rather than aqueous electrolyte are described in The 61/355 of U.S.Provisional Serial on June 15th, 61/383,510,2010 submission of the submission on the 16th of September in 2010, 081st, on Mays 11st, 61/329,278,2009 that on April 29th, 61/334,047,2010 that on May 12nd, 2010 submits to submit to The 61/267 of 7,61/177,072 and 2009 on the December submission submitted to, in 240, and is described in following United States Patent (USP) Shen Please in：The 13/105,794 of the submission of on May 11st, 2011；The 13/096,851 of the submission of on April 28th, 2011；April 13 in 2011 13/085,714 for submitting to day；And the 12/776,962 of the submission of on May 10th, 2010, the above-mentioned disclosure of each passes through Incorporated is incorporated herein.Essentially eliminate the solvent evaporation of electrolytic solution using low temperature or ionic liquid at room temperature in the battery Relevant problem.
Blomgren et al. describes the ionic liquid used in lithium ion battery as electrolyte substance（A.Webber, G.E.Blomgren,Advances in Lithium-Ion Batteries(2002),185-232;G.E.Blomgren, J.Power Sources2003,119-121,326-329）.Covalent Associates are described in WO01/93363 Noninflammability electrolyte, the electrolyte is made up of the salt with organic cation, or by ionic liquid, organic solvent, acrylic acid Ester polymer or fluoropolymer, and conducting salt composition.Yuasa companies describe non aqueous electrolysis in JP2002373704 Matter, its cyclic ester by 1- ethyl-3-methylimidazoles, lithium salts and with π keys is constituted.Mitsubishi Chemicals Industries Ltd. describe a kind of electrolyte in JP11307121, and it is by based on season imidazoles or season pyridinium ion Ionic liquid and 1% to 130 volumes % organic ring compound composition.The U.S. Patent number 7,960,061 of Jost et al. The ionic liquid as electrolyte substance is disclosed, disclosure of which is fully incorporated herein by reference.
Compound containing sulfonate ion is well known in the art.Many is referred to as the buffer agent of Good buffer agents Containing sulfonate ion.Some ionic liquids are known to contain specific sulfonate radical（Alkyl or aralkyl）Ion, such as trifluoromethyl Sulfonate radical.It is believed that not having to make with regard to the sulfonate ion with the more long alkyl chain replaced by amine or heteroaromatic group in the literature The description of the useful anion in for ionic liquid, the ionic liquid is useful in the application of electrochemical cell.
Ionic liquid at room temperature has extremely low steam pressure（The steam pressure of some substantially can not be surveyed at the standard conditions Amount）, therefore with little or no evaporation.Therefore, using low temperature or ionic liquid at room temperature as their ion conducting medium Battery need not be in order to make up the solution for including excessive bulk with the evaporation of time.The ionic liquid of relatively small amount be enough to prop up The electrochemical reaction needed for battery operation is held, so as to reduce battery weight and volume, and increases ratio of the power to volume/weight Rate.Furthermore, it is possible to avoid the other problemses relevant with solvent, such as the liberation of hydrogen in aqueous solution.The development of the creativeness is not recognized To be prior art, and only it is described within a context, in order to understand further development as herein described.
General introduction
It is R-SO that embodiments of the present invention are related to containing formula3 -Sulfonate ion and cation ionic liquid, wherein R It is substituted or unsubstituted with C2-C20The alkyl of carbon atom, the alkyl can together form ring.The other reality of the present invention The mode of applying is related to metal-air battery, and it includes the fuel electrode for oxygenated fuel, is configured to absorb and reduce gaseous oxygen Air electrode, and ionic liquid, the ionic liquid contains formula for R-SO3 -Sulfonate ion and cation, wherein R is to take In generation, is unsubstituted with C2-C20The alkyl of carbon atom, the alkyl can together form ring.Another embodiment party of the present invention Formula is related to the ion conducting medium itself for electrochemical cell.
Other purposes of the present invention, aspect and advantage will by detailed description below, accompanying drawing and appended claims Become apparent.
Brief Description Of Drawings
The present invention can obtain best by referring to the following description for illustrating embodiments of the present invention and accompanying drawing Understanding.
Fig. 1 is the schematic diagram of electrochemical cell according to the embodiment of the present invention.
Describe in detail
For the purpose of the application, low-temperature ion liquid is defined as having 150 DEG C under 1 atmospheric pressure or less than 150 DEG C The ionic liquid of fusing point.These low-temperature ionic liquids can also include the species for being considered as ionic liquid at room temperature, the room temperature Ionic liquid is defined as the ionic liquid under 1 atmospheric pressure with 100 DEG C or the fusing point less than 100 DEG C.Ionic liquid also by Referred to as liquid salt.Used as definition, ionic liquid is mainly made up of the anion and cation of salt.Simultaneously for be present in from One or more in sub- liquid other soluble products（Such as byproduct of reaction produced by additive or battery operation）, from Sub- liquid itself can be solvent, and ionic liquid need not be using solvent with dissolving salt, because the liquid is in itself " from dissolving ", i.e. it is that have the anion of the electrolytic salt and the liquid of cation based on its own property, and need not be made With single solvent with dissolving salt.
Even if however, be defined as low temperature or ionic liquid at room temperature by its fusing point each at 1 atmosphere pressure, one In a little embodiments, battery can run in the environment with different pressures, and therefore fusing point can be with operating pressure Change.Therefore, be used as defining the reference point of these liquid with reference to fusing point at 1 atmosphere pressure, and there is no suggestion that or Limit its actual service conditions in operation.Reference environment condition refers to 1 atmospheric pressure and room temperature.
In some non-limiting embodiments, the material that solvent is considered in some cases can be with relatively little of amount In being added to ionic liquid, either in order to improve ionic liquid in solute dissolubility（The additive of such as addition or due to Battery operates produced by-product in ionic liquid）Or in order to provide non-solvent function（For example promote some electrochemistry anti- Should or ion transport）.Therefore, not exclusively excluded using ionic liquid and may be considered in other cases solvent, or relatively For solute in ionic liquid as solvent material presence, but be because do not need solvent carry out dissolving ion liquid, It can be with relative to traditional electrolytic salt（It needs a large amount of solvents with dissolving salt itself, such as aqueous electrolyte solution）It is aobvious Write less amount to use.In fact, in some non-limiting embodiments, not using additional solvent to be possible.
In some non-limiting embodiments, the ion conducting medium between fuel and air electrode can be pure Low-temperature ionic liquids, i.e. it is made up of ionic liquid.In other non-limiting embodiments, it can substantially by ion Liquid is constituted, it means that for the purpose of the application, its can include ionic liquid and one or more not materially affect its As the other materials of ionic liquid characteristic.Therefore, term " being substantially made up of ionic liquid " clearly includes adding one kind Or multiple additives enter, to improve the ion transport function of ionic liquid, electrochemical reaction and/or the enhancing of the battery is supported Dissolubility of the solute in ionic liquid, but do not include that, using a large amount of solvents needed for the dissolving salt, such as aqueous electrolyte is molten The situation of liquid.Certainly, no matter in the embodiment being made up of ionic liquid or the basic embodiment being made up of ionic liquid, The presence of any byproduct of reaction or ion in ionic liquid will be allowed, because the essence of the ionic liquid is to promote this The ion of sample and/or the transport of by-product and/or formation.Term " solvent-free " or " lacking solvent ", can be used to characterize institute Ionic liquid is stated, and the term should be understood that（a）Only exclude by the purpose of dissolving ion liquid provide it is a large amount of molten Agent, and ionic liquid itself is not excluded for, the ionic liquid can be used as relative to another kind of material（Such as additive or battery are anti- Answer by-product）Solvent；And（b）One or more additive is not excluded the presence of, to improve the ion transport function of ionic liquid, Support the electrochemical reaction of the battery and/or improve dissolubility of the solute in ionic liquid, though in other cases or Relative to the solute in ionic liquid, this additive can be counted as in theory solvent, but the additive be not for The dissolving ionic liquid and function.For example, in some embodiments, water can with weight % of 10ppm to 95, or The level of weight % of 50ppm to 75 or weight % of 75ppm to 50 or less than 50 weight % is present, to support electrochemical reaction, Even if the water is without respect to ionic liquid such as its such act as solvents in other kinds of electrolyte, i.e. aqueous electrolyte Effect.
Ionic liquid typically refers to form the salt of the stable liquid comprising ion.That is, ionic liquid will be completely dissociated, base It is made up of negative, positive ion on this.Therefore, ionic liquid is natively conductive.Additionally, ionic liquid have insignificant vapour pressure, Low viscosity, wide liquidus curve scope（Up to 400 DEG C）, high thermal stability and big electrochemical window（>5V）.Due to these property Matter, ionic liquid generally will not evaporate in the charge/discharge cycle of electrochemical cell or be consumed.
Ionic liquid is typically present in two forms：It is proton type and aprotic.Proton type ionic liquid has can With the available proton being easily oxidized or reduced or can be coordinated with the anion of the oxygen being such as reduced.Proton type ionic liquid Some examples by anion tetrachloro aluminate, double（Trifluoromethyl sulfonyl）Acid imide, pyrovinic acid root, nitrate anion and acetic acid Root, and cation triethyl ammonium, diethyl first ammonium, dimethyl second ammonium, dimethyl ethyl trifluoromethanesulfacid acid ammonium, ethyl ammonium, α- Picoline, pyridine, and 1,8- pair（Dimethylamino）Naphthalene, 2,6- di-t-butyl pyridines, and guanidine（guanadines） Derivant combination synthesized by.But aprotic ionic liquid does not generally have proton activity.Aprotic room-temperature ion Some examples of liquid are by selected from chloride ion（Cl-）, hexafluoro-phosphate radical（PF6 -）, it is iodide ion, tetrafluoroborate, double（Trifluoromethyl Sulfonyl）Acid imide（C2F6NO4S2 -）（TFSI）, trifluoromethane sulfonic acid root（CF3O3S-）Anion, and selected from imidazoles, Synthesized by the combination of the cation of sulfonium, pyrrolidine, quaternary ammonium Huo quaternary phosphines and its derivant.It is non-proton although lacking proton activity Type ionic liquid can contain proton.For example, aprotic ionic liquid can contain at least one cation, and it has at least One strong bonding is to proton thereon.There is the selection of many other ionic liquids, and these examples be set forth in it is any In the case of it is all and nonrestrictive.
Embodiments of the present invention include ionic liquid, and the ionic liquid has 1mm Hg when higher than 20 DEG C of its fusing point Or less than the vapour pressure of 1mm Hg, preferably vapour pressure is 0.1mm Hg or less than 0.1mm Hg or 0 when higher than 20 DEG C of its fusing point Or substantially immeasurability.Ionic liquid at room temperature（“RTIL”）Be under 1 atmospheric pressure at 100 DEG C or less than 100 DEG C at form steady Determine the salt of liquid（That is, their fusing points under 1 atmospheric pressure are 100 DEG C or less than 100 DEG C）.For the purpose of the application, low temperature from Sub- liquid is defined as the ionic liquid under 1 atmospheric pressure with 150 DEG C or the fusing point less than 150 DEG C.Low-temperature ionic liquids also may be used With including various ionic liquid at room temperature.
But even if low temperature or ionic liquid at room temperature are defined by the fusing point of each of which under 1 atmospheric pressure, but one In a little embodiments, the battery can work in the environment with different pressures, and therefore the fusing point can be with work Make pressure and change.Therefore, it is related to the fusing point reference point for being construed as limiting these liquid under 1 atmospheric pressure, does not imply that or limit Make its use condition actual at work.
Generally, the pH of metal-air battery tends to rise in circulation, and depending on the charged state of the battery, electricity The organic component of solution matter may be exposed to superoxides, peroxide, hydrogen peroxide or other corrosive substances.In ILization The cation being widely present in（Such as 1,3- dialkylimidazoliums and N, N- dialkyl group pyrroles）And anion（Such as fluoroform Sulfonate radical and tfsi）It is little in both, if any, business-like metal-air battery is typically found in these In condition possess stability.
Meanwhile, the cation that those skilled in the art should predict is to these conditions by with steady better than average levelQualitative, it is little described in IL documents, or heretofore unknown.For example, 1- methyl isophthalic acids, 4- diazabicyclos [2.2.2] are pungent([C1ted]）, 1- ethyl -2,3- methylimidazoles（[C2dmim]）And tetramethyl-ammonium（[TMA]）As IL cationes not Such as studied abundant of such as 1,3- dialkylimidazoliums and N, N- dialkyl group pyrroles's cation.Additionally, imidazo [1,2-a] Pyridylium can be used as in said embodiment IL cationes.Although these cationes have desired chemical property, But they are typically unpractical as electrolyte, because, except [C2Dmim], when with known IL aniones（Such as fluoroform Sulfonate radical, tfsi, methanesulfonate）During pairing, they are usually formed undesirable high-melting-point salt.This tendentiousness is based on The IL of these cationes is not widely deployed one of reason.Dicyandiamide（[dca]）Be a few exceptions anion in one, When matching with it, these cationes define IL.
Embodiments described herein improves this feelings by expanding the available ion range for confirming to produce IL first Condition.What the embodiment was desirable to because they surprisingly and advantageously provide it is even listed above generally not The real IL preparations of practical cation.In addition, the embodiment is useful, because these ionic liquids can be used as other The non-aqueous bulk solvent of ionic liquid, described other ionic liquids for example, with business application in the unfavorable of electrochemical cell High-melting-point, or it is not intended to be used as the sole component of electrolyte in electrochemical cell.And, the system of the embodiment Agent generally remains the wide electrochemical window provided by the IL ions for more commonly existing, and in some cases, there is provided or even Broader electrochemical window.
Embodiments of the present invention include that containing formula be R-SO3 -Anion ion liquid, wherein R be replace or do not take Generation with C2-C20The alkyl of carbon atom, the alkyl can together form ring.Unsubstituted alkyl sulfonate radical is referred to as IL Anion, and in some embodiments, by the specifically exclusion from the present invention.The conjunction for using in a preferred embodiment Suitable sulfonate radical includes, such as hydroxyethylsulfonic acid. root（[ise]）, taurine root（[tau]）And Good buffer agents etc.（For example, 3- Morpholino propane sulfonic acid root（MOPS）, 4- (2- ethoxys) -1- piperazine propane sulfonic acid roots（HEPPS,EPPS）, the ethyl sulfonic acid of 1,4- piperazines two Root（PIPES）, N- (2- acetamidos) -2-aminoethyl sulfonic acid root（ACES）, N- cyclohexyl-Homotaurine root（CAPS）、 4- (2- ethoxys) -1- piperazine ethanesulfonic acid roots（HEPES）, 2- [(2- hydroxyls -1,1- double (methylol) ethyl) amino] ethyl sulfonic acid Root（TES）, N- [three (methylol) methyl]-Homotaurine root（TAPS）, 3- (N- tri- [methylol] methylamino) -2- hydroxyls Propane sulfonic acid root（TAPSO）.
Hydroxyethylsulfonic acid. root, or 2- ethylenehydrinsulfonic acid roots（C2H6O4S）It is known ion, its sodium salt is generally used for washing In agent strip soap and shampoo.Pentamidne Isethonate is known antibacterial.But hydroxyethylsulfonic acid. is had no knowledge about so far Root can form ionic liquid, not to mention in metal-air battery as ionic conduction liquid.In fact, due to hydroxyl Ethyl sulfonate has densification of charging, has the property of the overhead provision to hydrogen bond firmly and compared to normal alkyl sulfonate, will not Expected isethionate can form stable not to mention useful ionic liquid.Therefore, isethionate is used as steady Fixed and useful ionic liquid is the discovery that a unforeseeable discovery.
Known taurine root is collectively used for preventing arrhythmia with magnesium, it is possible to find in the medicine of wholistic therapy. Taurine root is one of naturally occurring sulfonic acid known to minority.Taurine root is had no knowledge about so far can serve as ionic liquid Anion in body, and based on the reason for really similar to hydroxyethylsulfonic acid. root situation, it is not expected that taurine root can shape Into stable not to mention useful ionic liquid.
3- morpholino propane sulfonic acid salt（MOPS）It is also known that be Good buffer agents, it is a kind of to be introduced in generation nineteen sixty by Good et al. Buffer agent.Good,Norman E.;et al.,“Hydrogen Ion Buffers for Biological Research,”Biochemistry5(2),pp467-77(1966).These buffer agents can be used for biological study and bioid Use in, including it in polyacrylamide gel electrophoresis is well known.They and similar compound are by expressing alkane The hetero atom labelling of base sulfonate radical.Can be used for the Good buffer agents and similar compound bag in preferred implementation known to other Include 2- (N- morpholinoes) esilate（MES）, 4- (2- ethoxys) -1- piperazine ethanesulfonic acid salt（HEPES）, 3- [4- (2- hydroxyl second Base) -1- piperazines] propane sulfonic acid salt（HEPPS）, N- cyclohexyl-Homotaurine salt（CAPS）, N- cyclohexyl -2- amino second sulphurs Hydrochlorate, 3- ﹛ [three (methylol) methyl] An Ji ﹜ propane sulfonic acid salt（TAPS）, 3- [N- tri- ﹛ methylols）Methylamino] sulphur of -2- hydroxyls third Hydrochlorate（TAPSO）, 2- ﹛ [three (methylol) methyl] An Ji ﹜ esilates（TES）, piperazine-N, N '-two (2-ethanesulfonic acid) （PIPES）Deng.The chemical formula of these buffer agents is as follows, wherein by remove the corresponding sulfonate radical of hydrogen evolution on OH it is cloudy from Son：
The ionic liquid of the embodiment includes sulfonate ion as above, and suitable cation.It is described Embodiment can use any cation, as long as it forms the ionic liquid of conduction together with azochlorosulfonate acid anion.Suitably Cation is those containing tertiary carbon, and it is quaternized and is subsequently converted to corresponding cation.Some representational sun Ion includes, but are not limited to pyrrolidines, piperidines, imidazoles, pyridines, morpholine class etc..Particularly preferred cation is 1, 4- diazabicyclos [2.2.2] octane（Also referred to as triethylenediamine, ted or）（It is Air The registered trade mark of the catalyst prod system including 1,4- diazabicyclos [2.2.2] octane of Products）1- alkyl derivatives Thing, especially 1- methyl isophthalic acids, 4- diazabicyclos [2.2.2] are pungent, 1- ethyl -2,3- methylimidazoles, N- ethyl-N- first Base morpholine, 1- Methylimidazole .s simultaneously [1,2-a] pyridine, tetramethyl-ammonium etc..According to provided herein is guideline, this area skill Art personnel are possible to provide suitably for the cation of azochlorosulfonate acid anion is to produce suitable ionic liquid.
In the zinc-air battery using ionic liquid electrolyte, water content is generally controlled to minimize the precipitation of hydrogen, Control plating form, and maintain the activity of water constant in battery.Electric discharge when, metal Zn fuel electrode be oxidized and It is completely solvated or is complexed in solution, in releases electrons into circuit.Meanwhile, molecular oxygen is reduced at air electrode, Consume those electronics in anode release.Once reaching the dissolubility of zinc ion, ZnO is deposited in battery.During charging, Zn2+Ion is in the moon（Fuel）Pole is reduced.Meanwhile, cause the oxidation reaction of molecular oxygen precipitation in air electrode.
In water-based metal-air cell, the oxidation reaction during charging at air electrode is only the oxidation of water.The reaction H is also resulted in addition to release oxygen+Ion migration passes through the battery.However, because zinc is anti-to hydrogen reduction in aqueous electrolyte Should have large overpotential, so can about 95% faradic efficiency.Faradic efficiency or current efficiency are electric charges（Electronics）In electricity The efficiency being transferred in chemical system.Electrical losses are typically by caused by participating in the electronics of unproductive reaction and short circuit.Hydrogen is also Original is the example of this unproductive reaction.Therefore, the large overpotential of the hydrogen reduction on zinc（That is, it is necessary for hydrogen reduction The potential barrier for overcoming）Mean that hydrogen reduction is unfavorable, it causes high faradic efficiency.
In a preferred embodiment some useful ionic liquids are allowed in 0.1-50%（Or even more high）Between The water of any amount enters zinc-air ion liquid cell, and the oxidation reaction during charging at air electrode is supported, i.e. water At oxygen electrode it is available for oxidation.Additionally, water destruct a small amount of in ionic liquid is in Aprotic media, height The well known Superoxide anion material produced by dismutation reaction in pKa conjugate acids and alkaline medium（HO2）Stability.
The additional benefit for adding water to ionic liquid is the H discharged from the oxidation reaction of water+Ion is of short duration, leniently will Electrolyte is acidified the solvation so as to promote ZnO to precipitate.More specifically, H+Ion can increase the acidity near ZnO precipitations, but Will not souring soln on a large scale.The solvation of ZnO can be described in following reaction：
(3)ZnO+2H+→Zn2++H2O
And, a small amount of water can be greatly reduced viscosity in ionic liquid, so as to cause the increase of electrical conductivity.
Additionally, the faradic efficiency in aqueous electrolyte is high（～95%）.Even without Ionic Liquids Ionic（Or Additive in battery）Specific adsorption be also such.High faradic efficiency in due to aqueous electrolyte, so having 5% to contain The ionic liquid electrolyte of the water yield is expected to have about 0.25% faraday to lose（5% water content * 5% loses=0.25%）.
In metal-air battery, metal is fuel.That is, during discharging, metal is oxidized in anode, carries Electronics for can be used for electric work.The oxidation reaction can be represented by equation below：
(3) metal → metaln++(n)e-
Metal fuel can be any types, and can be electrically deposited, absorb, physical deposition, or otherwise It is provided on fuel electrode or constitutes the fuel electrode.Fuel can be any metal, it may for example comprise alloy or its hydrogenation Thing.For example, fuel can include transition metal, alkali metal, alkaline-earth metal and other or it is " weak（poor）" metal.Transition metal bag Include but be not limited to zinc, ferrum, manganese and vanadium.The most frequently used alkali metal is lithium, but can be using other alkali metal.Other metals include But it is not limited to magnesium, aluminium plus gallium.As it is used herein, term metal fuel refers to any fuel including metal, including simple substance Metal, the metal being bonded in molecule or complex, the molecule or complex include oxide, metal alloy, metal hydride Thing etc..In some embodiments, fuel electrode can be formed by the metal fuel as electrode body itself.
Fuel electrode can have any configuration or configuration.For example, fuel electrode can be the hole with three-dimensional network, net Hole, the loose structure of multiple mesh being isolated from each other or any other suitable electrode.It can be independent entry that fuel electrode includes The current collector of part, or the main body of fuel is received thereon, it can be conductive and therefore be also current collector.In an embodiment party In formula, fuel electrode is laminated, is bonded or attached to provide the backing of fuel electrode outer surface.The backing can be liquid not It is permeable or substantially impermeable for ionic liquid, to prevent ionic liquid from passing through fuel electrode via its appearance Towards exosmosis.It is further preferred that the backing for air, especially oxygen or other oxidants be also it is impermeable, with Any undesirable parasitic reaction is prevented, such as the oxidant in the presence of oxidized occurred at electrode during discharging Reduction.
Can be in U.S. Patent Application No. 12/385,217,12/ about the more details of metal fuel and fuel electrode 385,489、12/885,268、12/901,410、12/631,484、12/549,617、13/019,923、13/028,496、61/ 193,540、61/301,377、61/323,384、61/329,278、61/365,645、61/394,954、61/358,339、61/ 383,510 and 61/243, find in 970, the above-mentioned application disclosure of each is herein incorporated by reference with its whole.
During discharging, the oxygen at air electrode is reduced, so as to consume electronics.For hydrogen reduction have it is several possible Mechanism.For example, oxygen reduction reaction can occur by one of three kinds of mechanism discussed below.However, depending on selectedization System（Ionic liquid, electrode material）, other mechanism can occur.
The first possible and non-limiting mechanism is four electronics oxygen reduction reactions（ORR）, wherein product is by completely also Former oxygen dianion.The four electronics oxygen reduction reaction can be represented by equation below：
(4)O2+2H2O+4e-→4OH-
Depending on the concrete chemical action of the system, the reaction can form soluble product or locally cause not The formation of solube metallic oxide.
In the reaction, the anion for being discharged can be used for adjusting ensuing anode reaction.Relative to other oxygen also There is former mechanism, four electronics oxygen reduction reactions increase energy density and each oxygen molecule to extract the excellent of the electronics of maximum quantity out Point.
Second possible and non-limiting mechanism is two electronics peroxide routes.The example of the mechanism can be by as follows Equation is representing：
(6)Zn2++O2+2e-→ZnO2
The mechanism has the advantages that relatively low overpotential to peroxide reactions.The mechanism is relative to the first mechanism Also tend to enhance rechargeablility.However, the two electronics peroxide mechanism causes in oxygen electrode relative to four electronic processes Relatively low energy density at battery.
The third possible and non-limiting mechanism be mixing two electronics/tetra- electronics ORR, its utilize some it is aliovalent sun from The reducing power of son.The example of the mechanism can be represented by equation below：
(7)Mn2++O2+2e-→MnO2
Nuance in the mechanism is that product includes the O for reducing completely by produced by the reducing power of aliovalent metal2- Class material.In this example, Mn2+Become the Mn on right side4+State.The mechanism has due to the reducing power of aliovalent cation There is relatively low overpotential.And, aliovalent metal can be used for manufacturing more effective battery.However, two electronics of the mixing/ Four electronic mechanisms cause relatively low energy density batteries relative to four electronic processes.
Air electrode is typically by such asPolitef（PTFE）Loose structure made by material.It is excellent Selection of land, air electrode material hates solvent borne for what electrolyte had a height.Solvent borne of hating in air electrode is played " protection against the tide " （Prevent liquid electrolyte from leaving battery）With improve the logical of the oxygen reduction reaction catalyst that oxygen in air is entered in loose structure The dual function in road.Due to the increase of the three-phase contact wire length of air-catalyst-electrolyte, hate solvent borne enhance into Enter the passage of catalyst.The increase of three-phase contact wire length reduces transmission and limits.Although hate by force solvent properties be it is favourable, However, include that solvophilic component improves the flexibility of three-phase contact in the electrodes, so as to improve the close of surface reaction site Degree.
Fig. 1 show according to embodiment of the present invention be generally designated as 10 low-temperature ionic liquids（IL）Electrochemical cell （" electrochemical cell "）.It is as shown below go out and describe, electrochemical cell 10 includes multiple electrodes, and the plurality of electrode includes the One electrode 12 and second electrode 14.In other embodiments, the first electrode or second electrode of electrochemical cell 10 can lead to Cross being configured to provide in addition to single electrode.In FIG in shown non-limiting embodiment, first electrode 12 is cloudy Pole, and more specifically air cathode, and hereinafter referred to as air electrode 12.Second electrode 14 is anode, and with Under will be referred to as metal electrode 14.In one embodiment, and as described below, electrochemical cell 10 can by with oxygen Reduction half-reaction of the agent 20 at air electrode 12 is parallel（I.e. substantially simultaneously）Oxidation of the fuel at metal electrode 14 Half-reaction is producing electricity.Shown embodiment is all not intended to be restricted anyway.
Air electrode 12 and metal electrode 14 are preferably spaced to form gap 16 therebetween.Ionic liquid at room temperature （RTIL）, it is indicated generally at digital 18, can flow so that RTIL18 can be while ingress of air electrode along gap 16 Both 12 and metal electrode 14.In one embodiment, it should be understood that electrochemical cell 10 can carry out by any way fixed To, and RTIL can be with the direction flowing in addition to shown direction.Therefore, any direction is referred to relative to institute in Fig. 1 The direction for showing is made, and is not intended to for the embodiment of work to be restricted to any specific orientation.In other embodiments, RTIL18 can be static, and not flow completely.RTIL18 can at air electrode/RTIL interfaces 24 with air electrode 12 Contact.RTIL18 can be contacted at metal electrode/RTIL interfaces 26 with metal electrode 14.In interchangeable embodiment, RTIL does not flow.That is, not including the mechanism for forced flow in battery.
In certain embodiments the preferably RTIL contains water, to promote the generation electrochemistry in electrochemical cell 10 anti- Should（Electric discharge in several cycles and charging）.Preferably, the amount of the ionic liquid including water be for about 15% to about 50%, it is more excellent Choosing about 20% to about 40% and most preferably from about 25% to about 30%.Not include need water with promote electrochemical reaction negative electrode and/ Or in the electrochemical cell 10 of anode, the preferably ionic liquid includes less than about 25% water, more preferably less than about 20%, or even More preferably less than about 15% water.According to provided herein is guideline, those skilled in the art are possible to determination and are included in basis Proper amount of water in RTIL prepared by the embodiment.
As mentioned above, reducing half-reaction can occur at air electrode 12.In one embodiment, aoxidize Agent 20 can be reduced by the reduction half-reaction at air electrode 12.For the purpose of non-limitative illustration, from metal electricity The electronics of pole 14 can flow external circuit 22（Load）And return to air electrode 12 to promote the reduction of oxidant 20. Oxidant 20 is reduced on air electrode 12 at oxidant reduction reaction site 21.In one embodiment, adopt and urge Agent is promoting the oxidant reduction half-reaction at oxidant reduction reaction site 21.Air electrode 12 can include catalyst Material（Such as manganese oxide, nickel, pyrolysis cobalt, activated carbon, silver, platinum or any other catalyst material or with for being catalyzed The mixture of the material of the high oxygen reduction activity of oxidant reduction）, this is discussed below.In one embodiment, Air electrode 12 can be the porous and porous body with high surface can include catalyst material.
In one embodiment, air electrode 12 can be passive or " breathing " air electrode 12, and its is passive Ground exposure（For example by window or opening）In oxidizer source（The oxygen being typically present in surrounding air）And absorb oxygen The consumption that agent 20 is used in electrochemical cell 10 reacts.That is, oxidant 20 will penetrate into sky from oxidizer source Pneumoelectric pole 12.Therefore, oxidant 20 need not on one's own initiative be pumped into or be otherwise oriented to air electrode 12, for example, pass through Entrance.Oxidant 20 by its absorbed or otherwise infiltration or ingress of air electrode 12 air electrode 12 it is any Part can be generally known as " input ".Term " input " can widely be included and for oxidant be transported to air electrode 12 Locate all modes for the oxidant reduction half-reaction at oxidant reduction reaction site 21 on air electrode 12.
By nonrestrictive explanation, air electrode 12 can be that the gas with the outer surface for being exposed to surrounding air can The electrode of infiltration so that oxidant 20 includes the oxygen for penetrating air electrode 12.Similarly, air electrode 12 may be embodied in sky The impermeable barrier film of gas-permeable and liquid of the outer surface of pneumoelectric pole 12, so as to allow oxidant 20 to pass through air electrode The infiltration of 12 outer surface, and prevent low temperature IL18 from flowing through the outer surface of air electrode 12.In one embodiment, air Electrode 12 can be the porous body covered by liquid-permeable layer in inner side, RTIL18 can by the liquid-permeable layer so as to Low temperature IL18 can contact porous body.
Relation between RTIL18 and air electrode 12 can affect the total energy density of electrochemical cell 10.Therefore, should This carefully selects the steam pressure and surface tension characteristics of RTIL18 according to air electrode 12.For example, in one embodiment, Air electrode 12 can repel RTIL and allow it to prevent RTIL18 wickings, i.e., air electricity is flow through in the way of class blood capillary Pole 12.In another embodiment, air electrode 12 can be designed with porous to absorb RTIL, so that it is for reality Now the purpose of the desired electrochemical reaction at air electrode 12 and low temperature IL is exposed to into the table of more air electrodes 12 Face region.Air electrode 12 can support that the catalyst at oxidant reduction reaction site 21 is modified to improve reaction efficiency. In one embodiment, can be using metal ion come modified catalyst, the metal ion can strengthen catalyst in catalysis The activity in oxidant reduction reaction on air electrode 12 at oxidant reduction reaction site 21.Air electrode 12 can have High ionic conductivity with provide reactant and from air electrode 12 remove oxidant reduction reaction product.In an embodiment party In formula, air electrode 12 can have high conductivity electronics is carried to into oxidant reduction reaction position from external loading 22 Point 21.The characteristic of air electrode 12 and RTIL18 can be further limited.
In one embodiment, metal-oxide by-product 28 can be formed at metal electrode 14.In view of aqueouss are electric The oxidizing agent ions that Xie Zhizhong is reduced are coordinated, that is, provide electronics feedwater molecule to form water, peroxide and/or hydrogen-oxygen Compound, so as to increase the problem relevant with steam pressure and corrosion, in this nonlimiting, RTIL18 can promote sky Oxidant reduction at pneumoelectric pole 12 reacts and the oxidizing agent ions being reduced is transmitted to into metal electrode 14.In order to support this As a result, RTIL18 can include the soluble substance interacted with the oxidizing agent ions being reduced, and RTIL18 is typically proton type 's.When the oxidizing agent ions being reduced move to metal electrode 14, RTIL18 can also support them.By means of non-limiting Illustrate, the migration of the oxidizing agent ions being reduced can refer to the oxidizing agent ions that are reduced by convection pass or conduction transmission or The transmission of diffusion transport.RTIL18 can also support to be retained in the oxidized metal-Fuel ion at metal electrode 14.At this In the case of kind, RTIL18 promotes the reaction between the oxidizing agent ions being reduced and oxidized metal-Fuel ion to produce Metal-oxide by-product 28.In one embodiment, metal-oxide by-product 28 can be stored in metal electrode At 14.Be stored in the embodiment at metal electrode 14 in metal-oxide by-product 28, the embodiment preferably by with Make once（It is i.e. non-chargeable）Battery, because oxygen is stored at metal electrode 14 and to for the oxygen class material that is reduced It is not available locally for the analysis oxygen electrode of oxidation.
Promote metal-oxide locally-stored in air electrode by air electrode 12, the air electrode 12 is extremely There is the aperture that be enough to that oxide is accommodated in the body of air electrode 12 in the region of few contact ions liquid.That is, aperture can take Certainly in the size of oxide.The network in this hole can increase the storage volume of air electrode 12.
In one embodiment, oxidizer source is surrounding air, and oxidant 20 is oxygen.In an embodiment In, can be reduced to be formed the oxonium ion that is reduced in air electrode 12 as the oxygen of oxidant 20.In an embodiment In, oxygen supply can be supplied from the oxygen recovery system of the precipitation for being used to regenerate electrochemical cell.Can be used for the reality of the invention of this paper Other examples for applying the electrochemical cell of mode are displayed in the U.S. Patent application 12/549 of such as 2009 on Augusts submission in 28, In 617, it is incorporated herein by with entire contents.
The electrolyte of the embodiment can be used for other battery structures.For example, a kind of interchangeable battery structure includes In U.S. Patent Application No. 61/267,240 and 12/776, the compact winding battery illustrated in 962, the patent application is whole with its Body is incorporated herein by.
Water electrolysis and self discharge during due to evaporating, recharging, aqueous electrolyte is for metal-air battery It is problematic.These problems do not only result in the loss of electrolyte, and cause the reduction of rechargeable battery cycle efficieny.Ion The use of liquid electrolyte reduces or may eliminate some problems in these problems.However, even with ionic liquid electricity Xie Zhi, the presence of water may cause the release of toxic gas and/or cause self discharge.On the other hand, enforcement of the invention The ionic liquid electrolyte of mode can include a small amount of water.For example, it has been found that the water content of 10-100ppm can improve non- The hydrogen reduction of Proton System, the release without causing unacceptable self discharge or toxic gas.Therefore, some embodiment party Formula includes the ionic liquid according to preparation described herein, wherein the ionic liquid contain about 5 to about 100,000ppm appoint The water of any quantity, more preferably from about 7 to about 1,000ppm water and most preferably from about 10 to about 100ppm water.In some embodiment party In formula, water can exist with the level of weight % of 10ppm to 95, or weight % of 50ppm to 75 or weight % of 75ppm to 50 or low In 50 weight %, to support electrochemical reaction, although its relative to ionic liquid be not as its in other kinds of electrolyte that Sample is used as solvent function.
All publications, patents and patent applications cited herein are incorporated herein by reference of text.
Article " a kind of (a, an) " is a kind of or more than one for referring to herein（That is, it is at least one）Article grammer Object.For example, " fluoropolymer resin " refers to a kind of fluoropolymer resin or more than one fluoropolymer resin.Cited herein is any Scope is all inclusive.The term " substantially " for using throughout the specification and " about " are used to describing and counting little ripple It is dynamic.For example, they can refer to less than or equal to ± 5%, e.g., less than or equal to ± 2%, such as less than or equal to ± 1%, such as less than or Equal to ± 0.5%, such as less than or equal to ± 0.2%, such as less than or equal to ± 0.1%, such as less than or equal to ± 0.05%.
The examples below being merely to illustrate property purpose is provided.Come using various cationes and the various aniones containing sulfonate radical Prepare ionic liquid.Test these ionic liquids stability in an electrochemical cell and practicality.As a result show, ionic liquid Can be used as the electrolyte in electrochemical cell.
Embodiment
Examples provided below is merely provided for illustrating the reaction principle of present embodiment, and should not be considered as Restricted.Conversely, the embodiment is intended to be included in all modifications within spirit and scope of the appended claims, replaces Change, change and equivalent.In the embodiment including Good buffer agents and related compound, identical is abridged for being conjugated Acid-Base To each member.Those skilled in the art will from the context recognize Good buffer agents or similar chemical combination Whether thing exists with conjugate acid or alkali.
Embodiment 1- prepare [C1ted][MOPS]
[C1Ted] [MOPS] be that, by cation 1- methyl isophthalic acid, 4- diazabicyclos [2.2.2] are pungent（[C1ted]）With the moon from Sub- 3- morpholinoes propane sulfonic acid root（[MOPS]）The ionic liquid of composition.
MOPS is sequentially loaded in the flask of 21.859-g（1.247g, 5.96mmol）[C1Ted] [OH] aqueous solution （0.92M, 6.480ml, 5.96mmol）.Remove water to generate [C by rotary evaporation1ted][MOPS]（1.996g, 100%, The water of nominal 0.15 weight %）, it is the ionic liquid of thick colorless.The ionic liquid of embodiment 1 is at ambient conditions liquid Body, electrochemical window during with platinum as working electrode with 7V.
Embodiment 2- prepares [C1ted][TAPS]
[C1Ted] [TAPS] be by C1Ted is used as cation and N- [three (methylol) methyl] -4- aminopropanesulfonic acids （TAPS）As the ionic liquid of anion composition.5.4342g TAPS is sequentially loaded in bottle（2.2398g, 9.2mmol）With [C1Ted] [OH] aqueous solution（0.92M, 10.0ml, 10.1906g, 9.2mmol）.The pH value of solution is shown on wide pH value reagent paper For 9-10.Take out aliquot（1.5984g, 12.9%）And concentrated with rotary evaporation, to generate [C1ted][TAPS] （0.4786g,>100%, the water of nominal 8 weight %）Ionic liquid.The ionic liquid of embodiment 2 is at ambient conditions liquid.
Embodiment 3- prepares [C1ted][ise]
[C1Ted] [ise] be by cation C1Ted and anion hydroxyethylsulfonic acid. root（ise）The ionic liquid of composition.Dress There is [C1Ted] [OH] aqueous solution（0.832M, 47ml, 39mmol）138.662-g list neck round-bottom flask be furnished with pH probes so that Probe extends to the below horizontal of batch of material.The sulphuric acid of about 10mL1.8M is added by the stirring near probe, pH is adjusted from 13.71 Save as 4.96.The mixture is concentrated as far as possible to leave 8.632 grams of residue by rotary evaporation, is nominally considered [C1ted]2[SO4]（6.853g, 100%）And water（1.779g）.Alcohol reagent（4mL）In adding the mixture so that it is nominally [C1ted]2[SO4] 2:Solution in 1 alcohol-water, is subsequently adding and is dissolved in the 2 of minimum:Hydroxyl in 1 alcohol-water (about 30mL) Ethylsulfonic acid sodium（5.869g, 40mmol）.By gained serosity stir about 2 hours, then suction strainer, as dense as possible by rotary evaporation Contracting filtrate.Residue is dissolved in into methanol（25mL）In, and it is loaded into the silica gel of the 230-400 mesh that about 20g is pre-installed in methanol Post on.
Slightly [C1Ted] the methanol solution air pressure of [ise] shifts level at the top of silica gel bed onto, while effluent In collecting the round-bottomed flask of 250ml；Flask methanol containing crude product before（25mL）Washing, the methanol equally quilt of washing Load and depress, while collecting effluent on the first fraction.Repeated washing process, until with fresh methanol（100ml）Punching Silicagel column is washed, while collecting effluent on the methanol solution of accumulation.By rotary evaporation concentrate merge methanol fraction with Generate [the C of purification1ted][ise]（8.56g, 34mmol, 87%）As ionic liquid.The ionic liquid of embodiment 3 is in environment Under the conditions of be liquid, there is the electrochemical window of 3V during with platinum as working electrode.
Embodiment 4- prepares [C2dmim][ise]
[C2Dmim] [ise] be by cation 1- ethyl -2,3- methylimidazoles and anion hydroxyethylsulfonic acid. root （ise）The ionic liquid of composition.Load [C in 250ml round-bottomed flasks2dmim]2[SO4]（7.331g, 21mmol）With 2:1 alcohol- Water（24ml）.Stirring mixture, until forming clear colorless solution, then disposably adds under agitation in mixture and prepares Good hydroxyethylsulfonic acid. sodium solution（6.267g, 42mmol）.Thin precipitation is subsequently quickly formed.By gained serosity stir about 2 Hour, then suction strainer, and filtrate is concentrated as much as possible by rotary evaporation.Residue is dissolved in into methanol（25mL）In, and load On the post of the silica gel of the 230-400 mesh being pre-installed in methanol to about 20g.
Such as embodiment 3, thick [C2Dmim] the methanol solution air pressure of [ise] shifts level at the top of silica gel bed onto, Effluent is collected the round-bottomed flask of 250ml simultaneously in；Flask methanol containing crude product before（25mL）Washing, washes The methanol washed equally is loaded and depresses, while collecting effluent on the first fraction.Repeated washing process, until with fresh Methanol（100ml）Rinse silicagel column, while except accumulation methanol solution on collect effluent.Closed by rotary evaporation concentration And methanol fraction generating [the C of purification2dmim][ise]（10.713g, 43mmol, 101%）As ionic liquid.Implement The ionic liquid of example 4 is at ambient conditions liquid.
Embodiment 5- [TMA] [ise]
[TMA] [ise] is by cation tetramethyl-ammonium（TMA）With anion hydroxyethylsulfonic acid. root（ise）The ion of composition Liquid.According to mode similar to Example 3, equipped with [TMA] [OH] 5H2O aqueous solutions（9.094g, 50mmol）Single neck circle Bottom flask is furnished with pH probes, so that probe extends to the below horizontal of batch of material.Add about 1.44M's by the stirring near probe Sulphuric acid（17.8ml, 26mmol）, pH is adjusted to 5.49 from 14.68, it is subsequently adding and is dissolved in the 2 of minimum:1 alcohol-water（About 40ml）In sodium isethionate（7.438g, 50mmol）.By gained serosity stir about 2 hours, then it was passed through by suction strainer Rotary evaporation concentrates as far as possible filtrate.Residue is dissolved in into methanol（25mL）In, and be loaded into about 20g and be pre-installed in methanol On the post of the silica gel of 230-400 mesh.
Such as embodiment 3, the methanol solution air pressure of thick [TMA] [ise] shifts the level at the top of silica gel bed onto, while In effluent being collected the round-bottomed flask of 250ml；Flask methanol containing crude product before（25mL）Washing, washing Methanol is equally loaded and depresses, while collecting effluent on the first fraction.Repeated washing process, until with fresh methanol （100ml）Silicagel column is rinsed, while collecting effluent on the methanol solution of accumulation.The first for merging is concentrated by rotary evaporation Alcohol fraction is generating [TMA] [ise] of purification（10.098g, 51mmol, 102%）As ionic liquid.The ion of embodiment 5 Liquid is at ambient conditions solid, is liquid when being put in the sample bottle being immersed in 80 DEG C of water-baths, is being held in environment It is liquid when in the room of the relative humidity on humidity but less than 40%RH.
Embodiment 6- [C1ted][EPPS]
[C1Ted] [EPPS] be by cation C1Ted and anion 4- (2- ethoxys) -1- piperazine propane sulfonic acid roots（EPPS） The ionic liquid of composition.According to the method similar mode with embodiment 2, in 5-g bottles EPPS is sequentially loaded into（2.3218g, 9.2mmol）[C1Ted] [OH] aqueous solution（0.92M, 10.0ml, 10.0643g, 9.2mmol）.Show on wide pH value reagent paper The pH value of solution is 9-10.Take out aliquot（1.5822g, 12.8%）And concentrated with rotary evaporation, to generate [C1ted] [EPPS]（0.4764g,>100%, nominal 6% water）As ionic liquid.The ionic liquid of embodiment 2 is at ambient conditions For liquid.The ionic liquid of embodiment 6 at ambient conditions for liquid and with platinum as working electrode when there is the electrification of 3V Learn window.
Embodiment 7- [C1ted][tau]
[C1Ted] [tau] be by cation C1Ted and anion taurine root（tau）The ionic liquid of composition.According to The method similar mode of embodiment 1, in the flask of 21.908g taurine is sequentially loaded into（0.996g, 7.96mmol）With [C1Ted] [OH] aqueous solution（0.92M, 8.649ml, 7.94mmol）.Remove water to generate [C by rotary evaporation1ted][tau] （1.884g, 94%, the water of nominal～6 weight %）As the ionic liquid of thick colorless.The ionic liquid of embodiment 7 is in environment Under the conditions of be liquid, there is the electrochemical window of 5V during with platinum as working electrode.
Embodiment 8- [C1ted][TAPSO]
[C1Ted] [TAPSO] be by cation [C1Ted] and anion 3- [N- tri- (methylol) methylamino] -2- hydroxyls third Sulfonate radical（TAPSO）The ionic liquid of composition.According to the method similar mode with embodiment 1, in the flask of 135.148g according to Secondary loading TAPSO（6.7432g, 26mmol）[C1Ted] [OH] aqueous solution（0.8M, 32.5ml, 26mmol）.Steamed by rotating Send out and remove water generating [C1ted][TAPSO]（10.370g, 95%, the water of nominal～5 weight %）As the ion of thick colorless Liquid.The ionic liquid of embodiment 8 is at ambient conditions liquid.
Embodiment 9- [TMA] [TAPSO]
[TMA] [TAPSO] is by cation [TMA] and anion 3- [N- tri- (methylol) methylamino] sulphur of -2- hydroxyls third Acid group（TAPSO）The ionic liquid of composition.According to the method similar mode with embodiment 1, fill successively in the flask of 64.125g Enter TAPSO（3.1121g, 12mmol）[TMA] [OH] aqueous solution（4M, 3ml, 12mmol）.By rotary evaporation remove water with Generate [TMA] [TAPSO]（4.127g, 97%, the water of nominal～3 weight %）As the ionic liquid of thick colorless.Embodiment 9 Ionic liquid at ambient conditions be liquid.
Embodiment 10- quaternary mixes IL
Quaternary mixes IL by [C1ted][MOPS]（Embodiment 1）、[C1ted][ise]（Embodiment 3）[C1ted] [tau]（Embodiment 7）（These three materials are as described herein to be prepared into ionic liquid）, and electro-chemical activity anion [OH] group Into.Mix IL to provide the mixture of the characteristic of the relative humidity of the solidification point with such as reduction and the deliquescence for reducing.Such as Embodiment 3 prepares [C as illustrating1Ted] [ise] and as aqueous solution（1.092M）Use.By the plastics to 5.6492g [C in centrifuge tube1ted][OH]（0.92M, 10ml, 9.2mmol）In sequentially add MOPS（1.9252g, 9.2mmol）To make Standby [C1Ted] [MOPS] and used with aqueous solution.[C in by from the plastic centrifuge tube to 5.5837g1ted][OH]（0.92M, 10ml, 9.2mmol）In sequentially add taurine（1.1516g, 9.2mmol）To prepare [C1Ted] [tau] and made with aqueous solution With.
By adding C in the plastic centrifuge tube to 5.4292g1ted][MOPS]（0.92M, 3.265ml, 3mmol）、 [C1ted][tau]（0.92M, 3.265ml, 3mmol）[C1ted][ise]（1.092M, 2.75ml, 3mmol）Prepare this three kinds The ternary equimolar mixture of IL.By the ternary mixture for rocking closed bottle to mix above-mentioned aqueous solution.So that [OH] account for the mode of 20 to the 80mol% of anion present in mixture mix the aqueous solution of the ternary mixture with [C1ted][OH]（3.5M, with oxidation zincification）, prepare so as to form quaternary mixture with [C1Ted] [OH] solution. Water is removed from the sample of quaternary mixture by rotary evaporation.The solution contains the water of 0 to 9 weight % and in environment bar It is liquid under part.
Sample is exposed to three days in the controllable air containing 5% relative humidity, does not show any solidification sign, and Pure [C1Ted] [OH] control sample solidifies.Subsequent test shows, with the nucleation site of promotion solidification in sample is added （The form of zinc silk and Zinc oxide powder）In the presence of, during being exposed to the time of 5% relative humidity more than 31 days, the mixing Thing is maintained as liquid.Electro-chemical test shows, in the 3V potential ranges on both zinc and platinum working electrode, the quaternary is mixed Compound is chemical and electrochemically stable.
Embodiment 11- [C1impd][ise]
[C1Impd] [ise] be by cation 1- Methylimidazole. simultaneously [1,2-a] pyridine [C1Impd] and anion ethoxy Sulfonate radical（ise）The ionic liquid of composition.From imidazo [1,2-a] pyridine and dimethyl sulfate according to following dialkyl group sulphuric acid The synthetic reaction of salt is preparing [C1impd]2[SO4]（3.166g, 8.74mmol）：
Wherein XR1……RyIt is imidazo [1,2-a] pyridine（impd）And RnOSO2ORzIt is dimethyl sulfate.
Product III is：
3- Methylimidazole .s simultaneously [1,2-a] pyridinium methosulphate
Product IV is：
3- Methylimidazole .s simultaneously [1,2-a] pyridinium methosulphate
Product V is：
3- Methylimidazole .s simultaneously [1,2-a] pyridinium methosulphate
Product V, [C1impd]2[SO4]（3.166g, 8.74mmol）It is dissolved in 2:1 alcohol-water（30ml）In, so The sodium isethionate for preparing is added thereto under agitation afterwards 2:1 alcohol-water（18ml）In solution（2.592g, 17.50mmol）.By gained serosity stir about 2 hours, then it was by suction strainer, and concentrates filtrate as far as possible by rotary evaporation.Will Residue is dissolved in methanol（25mL）In, and be loaded on the post of the silica gel of the 230-400 mesh being pre-installed in methanol of about 12g.
As in Example 3, thick [C1Impd] the methanol solution air pressure of [ise] shifts water at the top of silica gel bed onto It is flat, while in effluent being collected the round-bottomed flask of 250ml；Flask methanol containing crude product before（25mL）Wash Wash, the methanol of washing is equally loaded and depresses, while collecting effluent on the first fraction.Repeated washing process, until Use fresh methanol（125ml）Silicagel column is rinsed, while collecting effluent on the methanol solution of accumulation.It is dense by rotary evaporation It is condensed methanol fraction simultaneously to generate the [C of purification1impd][ise]（4.122g, 15.96mmol, 91%）As ionic liquid. The ionic liquid of embodiment 11 slowly solidifies at ambient conditions.More specifically, work as being included in the burning being immersed in 80 DEG C of water-baths It is the liquid for flowing freely during bottle；It remains liquid after a few houres are removed from water-bath.Afterwards, it is several in the liquid Region starts slowly to solidify independently of one another, and after probably about 1 day, the ionic liquid is changed into completely at ambient conditions solid.
Previous embodiment and embodiment are provided only for illustrating embodiments of the present invention, and should not It is considered as restricted.On the contrary, the embodiment be included in all modifications within spirit and scope described herein, Replace, change and equivalent.

Claims (12)

1. a kind of metal-air battery, it includes the fuel electrode for oxygenated fuel, is configured to absorb and reduce gaseous oxygen Air electrode, and the ionic liquid comprising at least cation and sulfonate ion, wherein the sulfonate ion is selected from hydroxyl second Base sulfonate radical ([ise]), taurine root ([tau]), 3- morpholinoes propane sulfonic acid root (MOPS), 4- (2- ethoxys) -1- piperazines third Sulfonate radical (HEPPS, EPPS), 1,4- piperazines diethyl sulfonate radical (PIPES), N- (2- acetamidos) -2-aminoethyl sulfonic acid root (ACES), N- cyclohexyl-Homotaurine root (CAPS), 4- (2- ethoxys) -1- piperazine ethanesulfonic acid roots (HEPES), 2- [(double (methylol) ethyls of 2- hydroxyls -1,1-) amino] ethyl sulfonic acid root (TES), N- [three (methylol) methyl] -3- aminopropan sulphurs Acid group (TAPS), 3- (N- tri- [methylol] methylamino) -2- hydroxy-propanesulfonic acid roots (TAPSO) and their mixture.
2. metal-air battery according to claim 1, wherein the sulfonate ion is hydroxyethylsulfonic acid. root.
3. metal-air battery according to claim 1, wherein the sulfonate ion is taurine root.
4. metal-air battery according to claim 1, wherein the cation is selected from alkyl-Isosorbide-5-Nitrae-diazabicyclo [2.2.2] it is pungent (alkyl-), 1- ethyl -2,3- methylimidazoles, N- ethyl-N-methylmorpholiniums, 1- Methylimidazole. simultaneously [1,2-a] pyridine, tetramethyl-ammonium and their mixture.
5. metal-air battery as claimed in claim 4, wherein the cation is 1- methyl isophthalic acids, 4- diazabicyclos [2.2.2] is pungent.
6. metal-air battery according to claim 4, wherein the cation is tetramethyl-ammonium.
7. metal-air battery according to claim 4, wherein the cation is 1- ethyl -2,3- methylimidazoles.
8. a kind of low-temperature ionic liquids under 1 atmospheric pressure with 150 DEG C or the fusing point less than 150 DEG C, it includes ethoxy sulphur Acid ion, and cation, the cation is selected from 1- methyl isophthalic acids, and 4- diazabicyclos [2.2.2] are pungent, 1- ethyl -2,3- Methylimidazole, N- ethyl-N-methylmorpholiniums, 1- Methylimidazole .s simultaneously [1,2-a] pyridine, tetramethyl-ammonium and they Mixture.
9. ionic liquid according to claim 8, wherein the cation is 1- methyl isophthalic acids, 4- diazabicyclos [2.2.2] is pungent.
10. ionic liquid according to claim 8, wherein the cation is tetramethyl-ammonium.
11. ionic liquids according to claim 8, wherein the cation is 1- ethyl -2,3- methylimidazoles.
A kind of 12. ion conducting mediums comprising ionic liquid for electrochemical cell, the ionic liquid is comprising as cloudy The hydroxyethylsulfonic acid. root of ion, and used as the 1- methyl isophthalic acids of cation, 4- diazabicyclos [2.2.2] are pungent.
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